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关于[Ru(NH3)6]3+与凝血酶结合适体序列形成的 G-四链体之间的相互作用。

On the interaction between [Ru(NH3)6]3+ and the G-quadruplex forming thrombin binding aptamer sequence.

机构信息

Chimie Analytique et Chimie des Interfaces, Faculté des Sciences, Université Libre de Bruxelles, CP 255, Boulevard du Triomphe 2, B-1050 Bruxelles, Belgium.

出版信息

J Inorg Biochem. 2013 Sep;126:84-90. doi: 10.1016/j.jinorgbio.2013.05.014. Epub 2013 May 30.

Abstract

The interaction between the thrombin binding aptamer (TBA), a G-quadruplex forming DNA sequence, and the electroactive hexaammineruthenium(III) cation has been studied by electrochemical methods and circular dichroism spectroscopy. When TBA is immobilised on a gold surface in a typical aptasensor configuration, the Ru(NH3)6 cation can be bound to the electrode surface through its interaction with the TBA sequence. This interaction is strong enough to enable the ruthenium complex to remain at the surface when the electrode is immersed in an electrolyte free of Ru(NH3)6, meaning that the complex does not diffuse back into the solution. A stoichiometry of 2 Ru(NH3)6 per TBA strand has been determined, indicating that the interaction differs from the conventional, non-specific electrostatic charge compensation, for which a 5 to 1 ratio would be expected between the triply charged cation and the 15 bases sequence. It is shown that this interaction takes place not only at the surface, but also when both TBA and hexaammineruthenium(III) are dissolved in solution. Under such conditions, a similar stoichiometry of 2 Ru(NH3)6 per TBA strand has been evidenced by two independent methods, namely circular dichroism spectroscopy and differential pulse voltammetry.

摘要

已通过电化学方法和圆二色光谱研究了凝血酶结合适体(TBA)与电化学活性六氨合钌(III)阳离子之间的相互作用。当 TBA 以典型适体传感器构型固定在金表面上时,Ru(NH3)6 阳离子可以通过与 TBA 序列的相互作用结合到电极表面。这种相互作用足够强,以至于当电极浸入不含 Ru(NH3)6 的电解质中时,钌配合物仍留在表面,这意味着配合物不会扩散回溶液中。已经确定了 2 Ru(NH3)6 与 TBA 链的化学计量比,表明这种相互作用不同于常规的非特异性静电电荷补偿,对于这种补偿,预期三价阳离子与 15 个碱基序列之间的比例为 5 比 1。结果表明,这种相互作用不仅发生在表面,而且当 TBA 和六氨合钌(III)都溶解在溶液中时也会发生。在这种情况下,通过两种独立的方法,即圆二色光谱法和差分脉冲伏安法,已经证明了类似的 2 Ru(NH3)6 与 TBA 链的化学计量比。

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